Polyurethane composition and molded article thereof

ABSTRACT

A polyurethane composition containing a urethane compound prepared by reacting 100 parts by weight of a polyol with a polyisocyanate such that the NCO/OH equivalent weight ratio is greater than 0.5 but less than 15, and an epoxidation product of a dimmer of a linear olefin compound having 6 to 30 carbon atoms, wherein the content of the compound (B) per 100 parts by weight of the polyol is greater than 5 parts by weight but less than 400 parts by weight.

This application is a continuation of U.S. Ser. No. 10/590,030 filedDec. 28, 2006, which is a 371 of PCT/JP05/01920 filed Feb. 9, 2005,which claims priority to Japan 2004-043973, filed Feb. 20, 2004, andJapan 2004-181161, filed Jun. 18, 2004.

FIELD OF THE INVENTION

The present invention relates to a polyurethane composition and a moldedarticle thereof.

TECHNICAL BACKGROUND

Polyurethane compositions can be diversely adjusted in chemical andphysical properties by combining, as required, a polyol, apolyisocyanate, a plasticizer and another additive. They are used invarious fields of soft to hard products such as an adhesive, a coatingcomposition, a fiber, a foam, a leather, a molded article, and the like.For polyurethane compositions, phthalic esters have been used as a cheapplasticizer for a long time.

However, with regard to the phthalic esters used as a conventionalplasticizer, there are suspicions that they are endocrine-disruptingchemicals, and it is required to place them under stringent control asfirst-category specified chemical materials under Pollutant Release andTransfer Register Law (PRTR Raw).

It is therefore demanded to develop a cheap and safe plasticizer thatreplaces such phthalic esters.

For example, there has been disclosed a polyester-based plasticizer as aplasticizer that is not any phthalic ester (JP-A-H2-160890). Further,there has been disclosed the use of diacetyl monoacyl glycerol as aplasticizer (JP-A-2002-129007). Further, there has been disclosed theuse, as a plasticizer, of a compound obtained by esterification of apolybasic acid and an alcohol having an ether bond (JP-A-2002-212534).However, the compositions containing such plasticizers are poor inworkability after prepared.

DISCLOSURE OF THE INVENTION

The present invention has been made in the light of the above problems,and it is an object of the present invention to provide a polyurethanecomposition with no suspicions that it contains an endocrine-disruptingchemical, and a molded article thereof.

For achieving the above object, the present inventors have made diligentstudies. As a result, it has been found that the use, as a plasticizer,of an aliphatic unsaturated hydrocarbon compound having at least onedouble bond is highly safe and produces a plasticization effect similarto those of conventional phthalic ester plasticizers (such as dioctylphthalate (DOP)), and the present invention has been accordinglycompleted.

According to the present invention, the following polyurethanecompositions are provided.

1. A polyurethane composition comprising (A) a urethane compoundobtained by reacting 100 parts by weight of a polyol with apolyisocyanate such that the NCO/OH equivalent weight ratio is greaterthan 0.5 but smaller than 15, and (B) a compound selected from a linearolefin compound having at least 6 carbon atoms, an oligomer of a linearolefin compound having at least 6 carbon atoms or an epoxy compound ofan oligomer of a linear olefin compound having at least 6 carbon atoms,wherein the content of said compound (B) per 100 parts by weight of saidpolyol is greater than 5 parts by weight but smaller than 400 parts byweight.2. A polyurethane composition as recited in 1, wherein the linear olefincompound having at least 6 carbon atoms for said compound (B) is anα-olefin having 6 to 30 carbon atoms.3. A polyurethane composition as recited in 1, wherein the linear olefincompound having at least 6 carbon atoms for said compound (B) is anα-olefin having 6 to 18 carbon atoms.4. A polyurethane composition as recited in 1, wherein the linear olefincompound having at least 6 carbon atoms for said compound (B) is alinear inner olefin having 6 to 30 carbon atoms.5. A polyurethane composition as recited in 1, wherein the oligomer of alinear olefin compound having at least 6 carbon atoms for said compound(B) is an oligomer formed of 2 to 8 molecules of a linear olefincompound having 6 to 30 carbon atoms.6. A polyurethane composition as recited in 1, wherein the epoxycompound of an oligomer of a linear olefin compound having at least 6carbon atoms for said compound (B) is an epoxidation product of a dimerof a linear olefin compound having 6 to 30 carbon atoms.7. A molded article produced by molding the polyurethane compositionrecited in any one of the above 1 to 6.

According to the present invention, there can be provided a polyurethanecomposition with no suspicions that it contains an endocrine-disruptingchemical, and a molded article thereof. The composition of the presentinvention is also excellent in workability after prepared.

PREFERRED EMBODIMENTS OF THE INVENTION

The polyurethane composition of the present invention comprises (A) aurethane compound obtained by reacting 100 parts by weight of a polyolwith a polyisocyanate such that the NCO/OH equivalent weight ratio isgreater than 0.5 but smaller than 15, and (B) a compound selected from alinear olefin compound having at least 6 carbon atoms, an oligomer of alinear olefin compound having at least 6 carbon atoms or an epoxycompound of an oligomer of a linear olefin compound having at least 6carbon atoms.

The urethane compound (A) is a polymer obtained by a condensativereaction of a polyol having at least 2 hydroxy groups (OH) with apolyisocyanate having at least 2 isocyanate groups (NCO).

The urethane compound (A) is obtained by reacting 100 parts by weight ofa polyol with a polyisocyanate such that the NCO/OH equivalent weightratio is greater than 0.5 but smaller than 15. When the NCO/OHequivalent weight ratio is 0.5 or less, the reactivity between thepolyol and the polyisocyanate is low, and no polyurethane compositioncan be obtained. When it is 15 or more, the compatibility of theurethane compound (A) with the compound (B) is poor.

In the present invention, when the composition is cured to form apolyurethane cured product, there is used, as a urethane compound (A), acompound obtained by reacting 100 parts by weight of a polyol with apolyisocyanate such that the NCO/OH equivalent weight ratio ispreferably greater than 0.5 but not more than 2.0, more preferably 0.9to 1.2.

When the composition is not cured to be a urethane prepolymer, there isused, as a urethane compound (A), a compound obtained by reacting 100parts by weight of a polyol with a polyisocyanate such that the NCO/OHequivalent weight ratio is preferably at least 2.0 but less than 15,more preferably from 2.0 to 10, still more preferably from 2.0 to 8.0.

As described above, the urethane compound (A) is produced whilecontrolling the amount of active (reactive with hydroxy group)isocyanate group of a polyisocyanate depending upon purposes.

Preferably, a polyol and a polyurethane are reacted in a nitrogen or dryair current at 70 to 100° C. for several hours.

A urethane prepolymer may be cured to form a polyurethane cured product.

The polyol is not specially limited so long as it is anactive-hydrogen-containing compound having two or more hydroxy groups.Generally, a polyether polyol or polyester polyol is preferably used.

More specifically, examples of the polyether polyol include diols suchas ethylene glycol, propylene glycol, butylene glycol, etc., triols suchas glycerin, trimethylolpropane, etc., and random or block copolymersobtained by ring-opening polymerization of propylene oxide and/orethylene oxide, etc., in the presence of one or more of ammonia andamines such as ethylenediamine, and the like.

Further, the polyester polyol includes copolymers obtained bypolycondensation of adipic acid, sebacic acid, terephthalic acid, etc.,in the presence of ethylene glycol, propylene glycol, 1,4-butanediol,neopentyl glycol, or the like.

Further, polyolefin-based polyols such as a polybutadiene-based polyol,polyisoprene-based polyol and hydrogenated products thereof are alsopreferred.

In addition to the above compounds, there can be usedlow-molecular-weight active hydrogen compounds having at least twohydroxy groups, such as bisphenol A, a rum ester of castor oil, and thelike. As such a compound, generally, there can be preferably used acompound having a molecular weight of 100 to 7,000 and having 2 to 4hydroxy groups per molecule.

The polyisocyanate is not specially limited so long as it has at leasttwo isocyanate groups.

Specifically, the polyisocyanate includes aromatic polyisocyanate suchas diphenyl methane diisocyanate (MDI), tolylene diisocyanate (TDI) andnaphthalene diisocyanate, aliphatic polyisocyanates such ashexamethylene diisocyanate (HDI) and lysine methyl ester diisocyanate,and alicyclic polyisocyanates such as hydrogenated diphenyl methanediisocyanate, isophorone diisocyanate, norbornane diisocyanate andhydrogenated tolylene diisocyanate. Of these, it is preferred to use MDIin view of toxicity, a price, and the like.

The compound (B) is selected from aliphatic unsaturated hydrocarbonshaving one or more double bonds. Specifically, it is selected from alinear olefin compound having at least 6 carbon atoms, an oligomer of alinear olefin compound having at least 6 carbon atoms or an epoxycompound of an oligomer of a linear olefin compound having at least 6carbon atoms. These compounds may be used singly, or as a mixture of atleast two members of these.

The linear olefin compound having at least 6 carbon atoms is preferablyan α-olefin having 6 to 30 carbon atoms, more preferably 6 to 18 carbonatoms. Examples thereof include 1-hexene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, etc.

A linear inner olefin having 6 to 30 carbon atoms is also preferred, anda linear inner olefin having 18 to 24 carbon atoms is more preferred.For example, 2-octadecene, 3-octadecene, 4-octadecene, 5-octadecene,2-eicosene, 3-eicosene, 4-eicosene and 5-eicosene are preferred. Theabove inner olefin refers to an olefin compound having a double bond ina position other than terminal positions. An inner olefin can beobtained by an isomerizing reaction, etc., of an olefin.

An aliphatic unsaturated hydrocarbon compound having two or more doublebonds is preferred since a non-conjugated compound has an excellentstability.

The oligomer of a linear olefin compound having at least 6 carbon atomsis preferably an oligomer formed of 2 to 8 molecules of a linear olefincompound. An oligomer formed of 9 or more molecules of a linear olefincompound is sometimes not suitable as a plasticizer since it has a highviscosity. When plasticization and a volatilization loss are togethertaken into account, oligomers including a dimer to a tetramer are morepreferred.

In this case, the number of carbon atoms constituting a linear olefinforming an oligomer is preferably 6 to 30, more preferably 6 to 18,still more preferably 10 to 15. Examples of the oligomer preferablyinclude 2-butyl-1-octene, 2-hexyl-1-decene, 2-octyl-1-dodecene,2-decyl-1-tetradecane, 2-dodecyl-1-hexadecane,2-tetradecyl-1-octadecane, a decene trimer, a decene tetramer, adodecene trimer, a dodecene tetramer, a tetradecene trimer, atetradecene tetramer, and the like.

The oligomer (dimer to octamer) of a liner olefin compound can beproduced in the presence of an acid catalyst or an organic metalcatalyst with a transition metal coordinated.

The epoxy compound of an oligomer of a linear olefin compound having atleast 6 carbon atoms can be produced by epoxidizing a linear olefincompound having at least 6 carbon atoms in the presence of an organicperacid such as peracetic acid or perbenzoic acid, a peroxide such asbenzoyl peroxide or methyl ethyl ketone peroxide, hydrogen peroxide, orthe like.

In the present invention, the above epoxy compound is preferably anepoxidation product of a dimer of a linear olefin compound having 6 to30 carbon atoms. Specifically, the epoxy compound can be preferablyselected from 2-butyl-2-hexyloxirane, 2-hexyl-2-octyloxirane,2-decyl-2-octyloxirane, 2-decyl-2-dodecyloxirane,2-dodecyl-2-tetradecyloxirane or 2-hexadecyl-2-tetradecyloxidane.

Further, a polyolefin compound such as a propylene oligomer or apolybutene oligomer can be also used.

The amount of the compound (B) per 100 parts by weight of the polyol isgreater than 5 parts by weight but smaller than 400 parts by weight,preferably 10 to 200 parts by weight, more preferably 40 to 150 parts byweight. When the above amount is 5 parts by weight or less, thecomposition has a high viscosity, and the workability thereof isextremely poor. When it is 400 parts by weight or more, the compositionis not cured, and no polyurethane composition is formed.

The composition of the present invention may contain other additives solong as the intended properties are not impaired. Specific examples ofthe additives include a filler, a thixotropy agent, a cure-promotingcatalyst, an adhesion-imparting agent, an antioxidant, a colorant, andthe like.

Specific examples of the filler include inorganic fillers having aparticle diameter of 1 to 500 μm such as clay, talc, calcium carbonate(bicarbonate, precipitated), calcium oxide, silica sand, a slate sandpowder, a mica powder, alumina, a glass powder, zinc flower, titaniumdioxide, carbon black, and the like, and inorganic fillers prepared bysurface-treating these. Of these, it is preferred to incorporate calciumbicarbonate in view of economics and easy handling. More preferably,calcium bicarbonate prepared by adjusting the moisture content ofcalcium carbonate to 0.1% or less is preferred. It is still morepreferred to incorporate one such calcium bicarbonate or two or morekinds of such calcium bicarbonates having different diameters.

The thixotropy agent specifically includes inorganic thixotropy agentssuch as a silica powder and an asbestos powder, and organic thixotropyagents such as organic bentonite, a polyvinyl chloride powder and amodified polyester polyol type agent. Of these, a silica powder ispreferred, which has a high thixotropy-imparting effect even when addedin a small amount.

The cure-promoting catalyst includes dibutyl tin dilaurate (DBTDL), leadoctylate, etc., and the adhesion-imparting agent includes couplingagents such as isocyanatesilane, glycidylsilane, and the like.

Further, there may be also used a hydrochloric acid absorbing agent, aheat stabilizer, a weathering stabilizer, a light stabilizer, anultraviolet absorbent, a slip agent, an anti-blocking agent, ananti-fogging agent, a lubricant, an antistatic agent, a flame retardant,a pigment, a dye, a dispersing agent, a copper toxicity inhibitor, aneutralizing agent, a foaming agent, a plasticizer, a gas foaminhibitor, a crosslinking agent, a flowability improving agent such asperoxide, a weld strength improving agent, a natural oil, a syntheticoil, a wax, and the like.

The composition of the present invention can be molded into variousmolded articles by methods of injection molding, extrusion molding,calender molding, coating, foaming, lamination, spinning, pressing,casting, and the like.

The composition may be dissolved, dispersed or emulsified in water, anorganic solvent, a mixture solvent of water and an organic solvent or amixture of two or more organic solvents to be used as a one-package ortwo-package type coating composition, adhesion, coating agent,scratch-inhibiting agent, or the like. The resultant solution,dispersion or emulsion may be applied by spraying, brushing,roll-coating, or the like.

EXAMPLES

The present invention will be explained more specifically with referenceto Examples hereinafter. Items in Tables were evaluated as follows.

(1) Measurement of hardness of polyurethane cured product: Measured witha durometer type A according to JIS K7215-1986.

(2) Presence or absence of bleed-out: A cured product was placed on afilter paper, and the filter paper was visually observed to determinewhether or not a plasticizer was adhered to the filter paper forevaluation of a presence or absence of bleed-out.

(3) Viscosity measurement: A composition containing a prepolymer wasmeasured for a viscosity with a Brookfield viscometer at 25° C.

(4) Compatibility: A composition containing a prepolymer was placed in abottle charged hermetically with nitrogen, and its appearance wasobserved for 1 month, for evaluation of compatibility. In this case, acomposition showing no phase separation was evaluated as ◯ (good), and acomposition showing a phase separation was evaluated as X (poor).

(5) NCO/OH equivalent weight ratio: Calculated from an NCO content of apolyisocyanate and an OH content of a polyol.

(6) Stability: Dioctyl phthalate (DOP) was evaluated as X since it issuspected to be an endocrine-disruptor, and a chlorinated paraffin wasevaluated as X since it contains a halogen.

Example 1

100 Parts by weight of a hydroxyl-group-terminated liquid polybutadienehaving an average molecular weight of 2,800 and a hydroxyl value of 46.6(mg-KOH/g) (trade name: Poly-bd R-45HT, supplied by Idemitsu Kosan Co.,Ltd.) was dehydrated, and then 12.6 parts by weight of liquid modifiedMDI (MDI: 4,4′-diphenylmethane diisocyanate) (trade name: MillionateMTL, supplied by Nippon Polyurethane Industry Co., Ltd.) (NCO/OHequivalent weight ratio=1.05), 50 parts by weight of 1-tetradecene(trade name: Linealene 14, supplied by Idemitsu Kosan Co., Ltd.) as aplasticizer and 0.05 part by weight of a curing catalyst (dibutyl tindilaurate (DBTDL)) were mixed therewith, to prepare a composition. Thecomposition was pressed with a hot press machine at 120° C. for 1 hourand then cured at 70° C. for 15 hours to give a polyurethane curedproduct.

Examples 2-6

A cured product was obtained in the same manner as in Example 1 exceptthat the plasticizer was replaced with 1-hexadecene (trade name:Linealene 16, supplied by Idemitsu Kosan Co., Ltd.) in Example 2, with adimer of 1-hexene (trade name: Alkylene 12, supplied by Idemitsu KosanCo., Ltd., purity of 95% or more) in Example 3, with a dimer of 1-decene(trade name: Alkylene 20, supplied by Idemitsu Kosan Co., Ltd., purityof 95% or more) in Example 4, with a trimer of 1-decene (trade name:Alkylene 30, supplied by Idemitsu Kosan Co., Ltd., purity of 90 wt % ormore) in Example 5, or with a tetramer of 1-decene (trade name: Alkylene40, supplied by Idemitsu Kosan Co., Ltd., purity of 90 wt % or more) inExample 6.

Comparative Example 1

A cured product was obtained in the same manner as in Example 1 exceptthat the plasticizer was not used.

Comparative Example 2

A cured product was obtained in the same manner as in Example 1 exceptthat the plasticizer was replaced with dioctyl phthalate (DOP) (specialgrade reagent, supplied by Hiroshima Wako Purechemical Ind., Ltd.).

Comparative Example 3

A cured product was obtained in the same manner as in Example 1 exceptthat the plasticizer was replaced with chlorinated paraffin (trade name:Toyoparax 145, supplied by Tosoh Corporation).

Comparative Example 4

Example 1 was repeated except that the amount of the liquid modified MDIwas changed to 6.0 parts by weight (NCO/OH equivalent weight ratio=0.5).In this Comparative Example, no cured product was obtained.

Comparative Example 5

Example 1 was repeated except that the amount of the plasticizer waschanged to 400 parts by weight. In this Comparative Example, no curedproduct was obtained.

Example 7

100 Parts by weight of polypropylene glycol having a molecular weight of3,000 (trade name: Adeka Polyether G-3000, supplied by Asahi Denka KogyoK.K.) was dehydrated, and then 15.5 parts by weight of a liquid modifiedMDI (NCO/OH equivalent weight ratio=1.05), 50 parts by weight ofLinealene 14 as a plasticizer and 0.05 part by weight of a curingcatalyst (DBTDL) were mixed therewith to prepare a composition. Thecomposition was cured at 70° C. for 24 hours to give a polyurethanecured product.

Examples 8-12

A cured product was obtained in the same manner as in Example 7 exceptthat the plasticizer was replaced with Linealene 16 in Example 8, withAlkylene 12 in Example 9, with Alkylene 20 in Example 10, with Alkylene30 in Example 11, or with Alkylene 40 in Example 12.

Comparative Example 6

A cured product was obtained in the same manner as in Example 7 exceptthat the plasticizer was not added.

Comparative Example 7

A cured product was obtained in the same manner as in Example 1 exceptthat the plasticizer was replaced with dioctyl phthalate (DOP) (specialgrade reagent, supplied by Hiroshima Wako Purechemical Ind., Ltd.).

Comparative Example 8

A cured product was obtained in the same manner as in Example 1 exceptthat the plasticizer was replaced with chlorinated paraffin (trade name:Toyoparax 145, supplied by Tosoh Corporation).

Tables 1 and 2 show evaluation results of Examples 1 to 12 andComparative Examples 1 to 8.

In Tables, the amount of each plasticizer is an amount per 100 parts byweight of a polyol.

TABLE 1 Examples 1 2 3 4 5 6 Polyol R-45HT R-45HT R-45HT R-45HT R-45HTR-45HT Polyisocyanate Modified Modified Modified Modified ModifiedModified MDI MDI MDI MDI MDI MDI NCO/OH    1.05    1.05    1.05    1.05   1.05    1.05 Plasticizer kind Linealene Linealene Alkylene AlkyleneAlkylene Alkylene 14 16 12 20 30 40 Amount 50 50 50 50 50 50 (part byweight) Hardness 40 32 43 28 25 24 Bleeding 24 hr No No No No No No  1week No No No No No No  4 weeks No No No No No No Safety ◯ ◯ ◯ ◯ ◯ ◯Comparative Examples 1 2 3 4 5 Polyol R-45HT R-45HT R-45HT R-45HT R-45HTPolyisocyanate Modified Modified Modified Modified Modified MDI MDI MDIMDI MDI NCO/OH    1.05   1.5    1.05   0.5    1.05 Plasticizer kind NoDOP Chlorinated Linealene Linealene paraffin 14 14 Amount  0 50 50 50400  (part by weight) Hardness 52 33 35 — — Bleeding 24 hr No No No — — 1 week No No No — —  4 weeks No No No — — Safety ◯ X X ◯ ◯

TABLE 2 Examples Comparative Examples 7 8 9 10 11 12 6 7 8 Polyol G-3000G-3000 G-3000 G-3000 G-3000 G-3000 G-3000 G-3000 G-3000 PolyisocyanateModified Modified Modified Modified Modified Modified Modified ModifiedModified MDI MDI MDI MDI MDI MDI MDI MDI MDI NCO/OH    1.05    1.05   1.05    1.05    1.05    1.05    1.05    1.05    1.05 Plasticizer kindLinealene Linealene Alkylene Alkylene Alkylene Alkylene No DOPChlorinated 14 16 12 20 30 40 paraffin Amount 50 50 50 50 50 50  0 50 50(part by weight) Hardness 25 21 26 22 20 19 35 22 24 Bleeding 24 hr NoNo No No No No No No No  1 week No No No No No No No No No  4 weeks NoNo No No No No No No No Safety ◯ ◯ ◯ ◯ ◯ ◯ ◯ X X

Examples 13-18

In Example 1, 24 parts by weight of 4,4′-diphenylmethane diisocyanate(MDI) (NCO/OH equivalent weight ratio=2.5) was used in place of theliquid modified MDI, 100 parts by weight of a plasticizer shown in Table3 and a catalyst were added, and the mixture was allowed to react in anitrogen current at 70° C. for 5 hours, to give a urethane prepolymer.

Examples 19-24

100 Parts by weight of polypropylene glycol having a molecular weight of3,000 (Adeka Polyether P-3000, supplied by Asahi Denka Kogyo K.K.) wasdehydrated, and then 20 parts by weight of MDI (NCO/OH equivalent weightratio=2.5), 100 parts by weight of a plasticizer shown in Table 3 and acatalyst were added. The mixture was allowed to react in a nitrogencurrent at 70° C. for 5 hours to give a urethane prepolymer.

Comparative Example 9

A urethane prepolymer was obtained in the same manner as in Example 13except that the plasticizer was not added.

Comparative Example 10

A urethane prepolymer was obtained in the same manner as in Example 13except that 145 parts by weight of MDI was used. The thus-obtainedprepolymer had poor compatibility with Linealene 14 (urethane prepolymerand Linealene 14 were separated), so that it was not measurable for aviscosity.

Comparative Example 11

A urethane prepolymer was obtained in the same manner as in Example 13except that the amount of the plasticizer was changed to 5 parts byweight. The thus-obtained prepolymer exhibited a high viscosity to suchan extent that it was not measurable with a rotational viscometer.

Comparative Example 12

A urethane prepolymer was obtained in the same manner as in Example 19except that the plasticizer was not added.

Tables 3 to 4 show evaluation results of Examples 13 to 24 andComparative Examples 9 to 12.

In Tables, the amount of each plasticizer is an amount per 100 parts byweight of a polyol.

TABLE 3 Examples Comparative Examples 13 14 15 16 17 18 9 10 11 PolyolR-45HT R-45HT R-45HT R-45HT R-45HT R-45HT R-45HT R-45HT R-45HTPolyisocyanate MDI MDI MDI MDI MDI MDI MDI MDI MDI NCO/OH   2.5   2.5  2.5   2.5   2.5   2.5    2.5 15 2.5 Plasticizer kind LinealeneLinealene Alkylene Alkylene Alkylene Alkylene No Linealene Linealene 1416 12 20 30 40 14 14 Amount 100  100  100  100  100  100  100 100  5  (Polymeri- zation amount) Viscosity (Pa · s) 80 65 85 60 64 72 200 NotNot measurable measurable Compatibility ◯ ◯ ◯ ◯ ◯ ◯ — X —

TABLE 4 Comparative Examples Example 19 20 21 22 23 24 12 Polyol P-3000P-3000 P-3000 P-3000 P-3000 P-3000 P-3000 Polyisocyanate MDI MDI MDI MDIMDI MDI MDI NCO/OH   2.5   2.5   2.5   2.5   2.5   2.5   2.5 Plasticizerkind Linealene Linealene Alkylene Alkylene Alkylene Alkylene No 14 16 1220 30 40 Amount 100  100  100  100  100  100  100  (Polymerizationamount) Viscosity (Pa · s) 40 33 42 27 31 36 90 Compatibility ◯ ◯ ◯ ◯ ◯◯ —

Example 25

A cured product was obtained in the same manner as in Example 1 exceptthat the plasticizer was replaced with an epoxidation product of dimerof 1-decene (2-decyl-2-octyloxirane, Alkylene 20 epoxide, supplied byIdemitsu Kosan Co., Ltd.). Table 5 shows composition and evaluationresults. The amount of the plasticizer in Table is an amount per 100parts by weight of a polyol.

TABLE 5 Example 25 Polyol R-45HT Polyisocyanate Modified MDI Plasticizerkind Alkylene 20 epoxide Amount (part by 50 weight) Hardness 29 Bleeding24 hr No 1 week No 4 weeks No Safety ◯

Example 26

100 Parts by weight of Alkylene 20 was added, as a plasticizer, to 100parts by weight of a urethane prepolymer (Colonate 4076, supplied byNippon Polyurethane Industry Co., Ltd.). The thus-obtained compositionwas evaluated for a viscosity (measurement temperature: 75° C.) andcompatibility. Table 6 shows components of the composition and theevaluation results.

The amount of the plasticizer in Table is an amount per 100 parts byweight of a polyol.

TABLE 6 Examples Comparative Examples 26 27 28 29 30 31 13 14 15Prepolymer Colonate Colonate Colonate Colonate Colonate ColonateColonate Colonate Colonate 4076 4076 4090 4090 4191 4191 4076 4090 4191Plasticizer kind Alkylene Alkylene Alkylene Alkylene Alkylene Alkylene —— — 20 20 20 20 20 20 epoxide epoxide epoxide Amount  100  100 100 100100 100 — — — (Part by weight) Viscosity (mPa · s) 1000 1100 490 500 200210 3000 1100 600 (at 75° C.) Compatibility ◯ ◯ ◯ ◯ ◯ ◯ — — —

Examples 27-31

Example 26 was repeated except that components for a composition werechanged as shown in Table 6. Table 6 shows the evaluation results.

Both Coronate 4090 and Coronate 4191 (trade names) are urethaneprepolymers supplied by Nippon Polyurethane Industry Co., Ltd.

Comparative Examples 13-15

Each of the urethane prepolymers used in Examples 26, 28 and 30 wasmeasured for a kinetic viscosity. Table 6 shows the results.

INDUSTRIAL UTILITY

The polyurethane composition of the present invention can be suitablyused in the fields of non-foamed polyurethane resins, such as anadhesive, a coating composition, a water-proofing agent, a sealant, aheat-insulating material, a low-temperature insulation material, acosmetic material, a sealing material, a magnetic binder, a cushioningmaterial, leather, a foam, a fiber, and the like. It is particularlypreferably used in the fields of an adhesive, a coating composition, awater-proofing agent and a sealant.

1. A polyurethane composition comprising: (A) a urethane compoundprepared by reacting 100 parts by weight of a polyol with apolyisocyanate such that the NCO/OH equivalent weight ratio is greaterthan 0.5 but less than 15, and (B) an epoxidation product of a dimmer ofa linear olefin compound having 6 to 30 carbon atoms, wherein thecontent of said compound (B) per 100 parts by weight of said polyol isgreater than 5 parts by weight but less than 400 parts by weight.
 2. Thepolyurethane composition according to claim 1, wherein the epoxidationproduct of a dimmer of a linear olefin compound having 6 to 30 carbonatoms (B) is selected from the group consisting of 2-butyl-hexyloxirane,2-hexyl-2-octyloxirane, 2-decyl-2-octyloxirane,2-decyl-2-dodecyloxirane, 2-dodecyl-2-tetradecyloxirane, and2-hexadecyl-2-tetradecyloxirane.
 3. The polyurethane compositionaccording to claim 1, wherein said polyol is selected from the groupconsisting of a polyether polyol, a polyester polyol, a polyolefin-basedpolyol, bisphenol A, and a rum ester of cator oil.
 4. The polyurethanecomposition according to claim 1, wherein said polyol is polypropyleneglycol.
 5. The polyurethane composition according to claim 1, whereinsaid polyisocyanate is selected from the group consisting of an aromaticpolyisocyanate, an aliphatic polyisocyanate, and an alicyclicpolyisocyanate.
 6. The polyurethane composition according to claim 1,wherein said polyisocyanate is diphenyl methane diisocyanate (MDI). 7.The polyurethane composition according to claim 1, wherein the contentof said compound (B) per 100 parts by weight of said polyol is greaterthan 40 parts by weight but less than 150 parts by weight.
 8. Thepolyurethane composition according to claim 1, further comprising one ormore additives selected from the group consisting of a plasticizer, acure-promoting catalyst, a filler, a thixotropy agent, anadhesion-imparting agent, an antioxidant, and a colorant.
 9. Thepolyurethane composition according to claim 8, wherein said plasticizeris present in the polyurethane composition and is selected from thegroup consisting of 1-tetradecene, t-hexadecene, a dimer of 1-hexene, adimer of 1-decene, a trimer of 1-decene, and a tetramer of 1-decene. 10.The polyurethane composition according to claim 8, wherein said curingcatalyst is present in the polyurethane composition and is dibutyl tindilaurate.
 11. A molded article prepared by molding the polyurethanecomposition according to claim 1.